Review on Rare Earth/Polymer Composite

The special properties of rare earth/polymer composite were described. More emphasis was put on the radiation shielding and magnetic properties. In the application to X-ray shielding, rare earth/polymer composite can make up the feeble absorbing area. If the rare earth content is high enough, it can demonstrate strong ability for thermal neutron absorption; The composite has strong paramagnetism. The feasibility of preparing magnetic rare earth/polymer composite was discussed. In addition, three preparation methods were introduced: simple polymerization, mixing and reaction processing. The effect of the rare earth/polymer composites pre-sturcture and the coordinate number of rare earth ions on the light property was analyzed. Rare earth/polymer composite may have the structure and property simlar to those of the ionomer. The feasibility of the in-situ preparation of the rare earth/polymer nano structure is indicated. Besides, the relationship between structure and properties of the rare earth/polymer composite was discussed. The problems associated with such composite materials were also presented.

CATALYTIC ACTIVITIES OF RARE-EARTH CALIXARENE COMPLEXES IN POLYMER SYNTHESES

The studies of our group on the catalytic activities of rare earth calixarene complexes in polymer syntheses are reviewed. Rare earth calixarene complexes are effect catalysts for the polymerizations of butadiene, isoprene, ethylene, styrene, propylene oxide, styrene oxide, trimethylene carbonate and 2,2-dimethyl-trimethylene carbonate.

A series of rare earth coordination polymer constructed from paddle-wheel building blocks

Three coordination polymers, Ln2（bpdc）3（phen）2（H2O）2 （Ln=Nd（1）, Eu（2）, and Tb （3）; bpdc=2,2＇-bipyridine-3,3＇-dicarboxylate; phen=1,10-phenanthroline）, were obtained by hydrothermal reaction of Ln2O3 with 2,2＇-bipyridine-3,3＇-dicarboxylate acid, and 1,10-phe- nanthroline. They were characterized by single-crystal X-ray diffraction, IR spectra, and photoluminescent spectra. The crystallographic data of 1-3 indicated that they were isostructural. Both complexes contained paddle-wheel building blocks, formed by bpdc and phen ligands. These paddle-wheel secondary building units （SBUs） were further connected to form two-dimensional （2-D） metal organic framework （MOF） networks by 2,2＇-bipyridine-3, and 3＇-dicarboxylate tinkers. A three-dimensional （3-D） supramolecular structure was formed by π-π aromatic interactions between adjacent 2-D infinite networks. Photoluminescent measurements indicated that europium compound 2 and terbium compound 3 were strong, red and green emitters, respectively.

Preparation and properties of polymeric colloidal crystals containing rare earth complexes

Rare earth organic complexes were introduced into the polymerization system, and the polymeric colloidal nanospheres containing rare earth complexes were prepared by emulsion copolymerization. The characterization results indicated that the polymeric spheres were small at nanometer size and the diameter was monodisperse, particularly the nanospheres possessed good fluorescent properties. Moreover, the polymeric nanospheres were self-assembled to fabricate the colloidal crystals, which were three-dimensional regular multilayer films. The polymeric colloidal crystal films exhibited excellent luminescent and novel optical properties.

Synthesis, Characterization of A Novel Polymeric Reaction Monomer for Preparing Highly Fluorescent Rare Earth Polymer Materials

A novel polymeric reaction monomer (NPRM) for preparing highly fluorescent rare earth polymer materials was synthesized via interface and coordinating reaction. The composition and structure of the NPRM and intermediate product (ligand) were characterized through the Fourier transform infrared spectroscopy (FT-IR), carbon-nuclear magnetic resonance spectrum (13CNMR), Mass spectra (MS), and element analysis data. The results showed that the composition and structure of NPRM agreed with that of anticipated product. The NPRM was composed of two important sections. Section 1 was able to provide excellent fluorescent properties for final rare earth polymer material through the effect energy transfer between ligand and rare earth ion; Section 2 would endow with the NPRM excellent polymeric active and form highly fluorescent rare earth polymer material. Fluorescent properties of the NPRM were also researched via a CARY ECLIPSE fluorescent spectrometer. The results showed that the NPRM possessed excellent luminescent properties. The corresponding emission peaks based on the 5D0→7F1(601.6 nm), 5D0→7F2(625.0 nm), 5D0→7F3(660.5 nm) and 5D0→7F4(706.3 nm) transitions for Eu3+ were observed. The strongest emission peak was at 625 nm, which belonged to 5D0→7F2 transition.

RARE EARTH CONTAINING POLYMER TERNARY COMPLEXES AND THEIR FLUORESCENT PROPERTIES

Rare earth containing fluorescence active polymer ternary complexes were synthesized and their absorption and emission properties were investigated.

POLYMER-SUPPORTED RARE EARTH CATALYSTS FOR STYRENE POLYMERIZATION

The neodymium complex supported on styrene-maleic anhydride copolymer (SMA·Nd) has been prepared for the first time and found to be a highly effective catalyst for the polymerization of styrene. The SMA·Nd polymeric complex is characterized by IR and its catalytic activity, and the polymerization features have been investigated in comparison with that of the conventional Ziegler-Natta catalysts. When [Nd]=1×10^(-3) mol/L, [M]=5mol/L, Al/Nd=170(mol ratio) and CCl_4/Nd=50(mol ratio), the polymerization conversion of styrene gets to 51.6% in six hours, and the catalytic activity reaches 1852 gPS/gNd, which is much higher than that of conventional rare earth catalysts. The polymerization reaction has an induction period and shows some characteristics of chain polymerization. The polymerization rate is the first order with respect to the concentration of styrene monomer. Addition of FeCl_3 does not suppress the polymerization.

Preparation and Characterization of Polymer－Supported Rare Earth Complexes

he polymers containing different ligand groups of atoms(mainly O,N,and S)and their rare earth complexes were prepared,characterized and classified based on the type of metal-ligand bonding. The catalytic activities of the complexes are briefly discussed.The polymer- supported rare earth complexes shwed much greater activities than the correspond- ing complexes with a low molecular weight.

A REVIEW ON THE ENHANCED PERFORMANCE OF POLYMER MATERIALS BY INTEGRATING RARE EARTH

Due to excellent, unique and safe properties of rare earth, it is a common method to integrate rare earth with polymer matrices so as to confer their fascinating and complementary properties to the polymer materials, in order to create new composite materials with special properties such as mechanical, thermal, antioxidative, flame retardant, antibacterial properties, etc. Generally speaking, rare earth just plays a synergistic effect on metal oxide and organic ligands. The rare earth addition usually does not exceed 10%.This article is to provide a comprehensive and up-to-date overview for rare earth synergistic effect on the properties of polymers, and present the application of rare earth in improving the properties of polymers.

Preparation and Properties of Rare Earth Modified Carbon Black/Natural Rubber Composites

The oxides Eu, Ho, Er and Dy were used to prepare the hydroxides of rare earth modified carbon black. Then natural rubber latex （NRL） was added into the reactor. The system reacted at 85 ℃ with stirring for 1 h to prepare powdered HAF-Ln（OH）3/NR composites. The effects of the kind and content of Ln on the particle size distribution of P [ NR/HAF-Ln （OH）3 ] and mechanical properties of its vulcanizate were studied respectively. It is found that rare earth can help to get the powder of the composite, the product particle with a diameter less than 0.9mm will be get when the composites containing the compound of Ho, Er and Dy with dosage of 1.0, 1.0, O. 5 percent, respectively. The adding of Ln can improve the tensile strength and tear strength of the vulcanizate effectively, what＇s more, Er and Dy can decrease the permanent set of vulcanizate significantly. The SEM studies shows that P[ NR/HAF-Dy （OH）3 ] vulcanizate shows superior mechanical properties that depend primarily on the absence of free carbon black, the fine dispersion of carbon black in the rubber matrix and better polymer-filler interaction.

Synthesis, Crystal Structure and Fluorescent Properties of a New One-Dimensional Polymer [Sm(sal)_4(phen)_2Na]_n

The title complex, [Sm(sal)_4(phen)_2Na]_n (Ⅰ), where Hsal=salicylic acid, phen=1, 10-phenanthroline, was synthesized by the reaction of samarium chloride with phen and Hsal in ethanol solution and its crystal structure was determined by X-ray diffraction. The crystal is monoclinic, space group C2/c with cell dimensions of a=2 84989 (7) nm, b=0 93347 (2) nm, c=2.27954 (5) nm, β=132.4010 (8)°, V=4.4781 (2) nm^3, Z=4, μ (Mo Kα)=13.97 cm^(-1), D_c=1.605 g·cm^(-3). The title complex is a compound, with centre of the Sm and Na atoms which are bridged by two carboxylate ligands. The structure of the complex demonstrates one-dimensional chain bridged by carboxyl groups. The fluorescence spectrum of the complex indicates that the second ligand phen shows enhancement effect on the fluorescence of the complex.

Preparation and properties of RE^(3+) doped luminescent co-polymer by solution copolymerization

Bonded type RE3+ doped luminescent co-polymer was synthesized by solution free radical copolymerization. The influence of charge sequence, monomers and co-polymerized method on properties and structures of the co-polymers was studied. The emission intensity of the co-polymers at different RE3+ concentrations was tested. The results showed that the co-polymers of Eu-PSt and Eu-PMMA both had wide absorption peak at 200-400 nm and the strongest peak appeared at 235 nm. The fluorescent intensity of Eu3+ doped polystyrene co-polymer was stronger than that of Eu3+ doped PMMA copolymer. The characteristic emission of europium ions was observed in the co-polymers. The copolymer doped with rare earth elements showed the 'sensitization effect' for the central ions. The bonded-type rare earth copolymer not only enhanced the energy transfer efficiency, but also improved the fluorescence intensity by increasing the rigidity of main and side chain.

Hydrothermal synthesis and structural studies of a new coordination polymer of lanthanum(Ⅲ) with benzene-1,2,4,5-tetracarboxylic acid and 4,4′-bipyridine

A new lanthanum complex formulated as {（bpyH2）[La（btc）（H2O）4（NO3）]·2H2O}n （1） （btcH4=benzene-1,2,4,5-tetracarboxylic acid; bpy=4,4＇-bipyridine） was hydrothermally synthesized. The complex was characterized by FT-IR spectroscopy, elemental analysis and X-ray diffraction. X-ray crystal structural analysis revealed that the compound belonged to the monoclinic space group C2/c with cell parameters a= 1.42806（7） nm, b=1.10258（5） nm, c=1.60333（8） nm and β=101.9400（10）°. The complex was polymeric with La^III atoms linked by four O atoms from two carboxylate groups of one benzene-1,2,4,5-tetracarboxylate. The LaIn atom was ten coordinated in a distorted tetracapped trigonal prism. In the crystal structure, a wide range of noncovalent interactions consisting of hydrogen bonding （of the types of O-H…O, N-H…O and C-H…O） and ion pairing interactions connected the various components into a supramolecular structure.

Study on Synthesis and Polymerization of Mono (isopropylmaleate oyloxyl) Diisopropoxyl Dysprosium

Mono(isopropyl maleate-oyloxyl) diisopropoxyl dysprosium(DM) was synthesized by the reaction of dysprosium isopropoxide with maleic anhydride. Dy-containing polymer(PDM) was obtained by the solution polymerization of DM using 2, 2'-azobisisobutyronitrile (AIBN) as an initiator. The kinetic study on the polymerization shows that the polymerization of DM exhibits high apparent activation energy(96.3 kJ.mol(-1)), indicating that the activity of DM is low for polymerization. The kinetic equation of polymerization can be expressed as R-P = k(P)C(DM)(1.23)c(AIBN)(0.82). The polymeric solid material shows excellent heat-stability and strong characteristic fluorescence of Dy3+, (4)Fg(9/2) --> H-6(15/2) and F-4(9/2) --> H-6(13/2).

Preparation and Compressive Stress Effect of Polymer Matrix RE-Fe Giant Magnetostrictive Composite

Polymer matrix RE-Fe giant magnetostrictire composite （GMPC） was prepared using bonding and magnetic field forming technique, and magnetostriction of samples was measured for different compressive stress. The experimental results show thai there is certain compressive effect in GMPC. And the influence of compressive stress on magnetostriction of sample was investigated. It offers essential reference for application and device design of GMPC.

Synthesis and Structures of Three Erbium(Ⅲ) Dicarboxylate Coordination Polymers

Three polymeric erbium(Ⅲ) complexes [Er(oba)(Hoba)(H 2O) 2]H 2O (A),[Er 2(oba) 3(H 2O) 4] (B), [Er 2(oba) 3(2,2′ bpy) 2] (C) (H 2oba=4,4′ oxybis(benzoic acid), 2,2′ bpy = 2,2′ bipyridine) were hydrothermally synthesized by altering the metal/carboxylate ratios or in the presence of an additional chelate 2,2′ bpy ligand, and characterized by single crystal X ray diffraction. The results show that different metal/carboxylate ratios can influence the polymeric structures and the presence of 2,2′ bpy ligand alters the topology of the framework from two dimensional to three dimensional.

SYNTHESIS AND IDENTIFICATION OF CONDUCTING POLYANILINE DOPED WITH RARE EARTH CHLORIDE

Polyaniline doped with rare earth chloride was synthesized in organic solvent and identified by elemental analysis and infrared spectroscopy. The experimental results show that there exists both doping and complexation at the same time in the resulting product. When pH4. Moreover, polyaniline doped with rare earth chloride exhibits better thermal stability than that doped with hydrochloric acid.

Synthesis and Catalytic Activities of Polymer-Supported Neodymium Complexes——Polymers Containing Thiol and Sulphoxide

The neodymium complexes with crosslinked polystyrene containing -CH2SH and -CH2SOCH3 groups, P-CH2SH . NdCl3 and P-CH2SOCH3. NdCl3, were prepared. P-CH2SH . NdCl3 shows no catalytic activity for butadiene polymerization, while P-CH2SOCH3. NdCl3 can catalyze the polymerization of butadiene. The content of cis-1,4-polybutadiene is more than 95%.

Synthesis of ion imprinted polymers for selective recognition and separation of rare earth metals

Lanthanide-ion imprinted polymers（L-IIPs） were synthesized by stoichiometric amounts of rare earth ions and the cavities in the polymers were created for the corresponding lanthanide ions. The maximum sorption capacities were estimated to be 125.3, 126.5, 127.6, 128.2 and 129.1 mg/g for Pr, Nd, Sm, Eu and Gd, respectively at p H 6. In the selectivity study, the L-IIPs exhibited good selectivity to the specific rare earth ions in the presence of coexisting cations. The imprinting results were found to be excellent with some rare earth ions over other competitor rare earth ions with the same charges and close ionic radius.

A novel polystyrene-poly(hydroxamic acid)interpenetrating polymer network and its adsorption towards rare earth ions

A novel polystyrene-poly(hydroxamic acid)interpenetrating network resin(PS-PHA IPNs)was successfully synthesized by suspension polymerization and interpenetrating network technology.The effects of various experimental parameters,including pH,contact time and initial concentrations of rare earth ions on the adsorption capacity were discussed in detail.Under the condition of pH 4.0(La^(3+)),1.0(Ce^(3+))and 3.0(Y^(3+)),respectively,PS-PHA IPNs can reach equilibrium adsorption in 6 h and get maximum adsorption capacities(1.08,1.43 and 1.36 mmol/g).The adsorption process of PS-PHA IPNs for La(Ⅲ),Ce(Ⅲ)and Y(Ⅲ)ions can be described by liquid membrane diffusion,particle diffusion and chemical reaction.The adsorption process is a spontaneous and endothermic process and can be better simulated by Langmuir adsorption isotherm.The studies of SEM-EDS indicate that rare earth ions are adsorbed on the surface of PS-PHA IPNs.Fourier transform infrared spectroscopy(FTIR)and X-ray photoelectron spectroscopy(XPS)analysis further prove that rare earth ions are chemisorbed on the surface of PS-PHA IPNs.These results reveal that the as-prepared PS-PHA IPNs is a promising adsorbent for adsorption of rare earth ions due to their higher adsorption capacity than other adsorbents.